| 1. |
- Abdurrokhman, Iqbaal, 1991, et al.
(författare)
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Binary Mixtures of Imidazolium-Based Protic Ionic Liquids. Extended Temperature Range of the Liquid State Keeping High Ionic Conductivities
- 2022
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Ingår i: Frontiers in Chemistry. - : Frontiers Media SA. - 2296-2646. ; 10
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Tidskriftsartikel (refereegranskat)abstract
- Binary mixtures based on the two protic ionic liquids 1-ethylimidazolium triflate ([C2HIm][TfO]) and 1-ethylimidazolium bis(trifluoromethanesulfonyl)imide ([C2HIm][TFSI]) have been investigated, with focus on phase behavior, ionic conductivity, and intermolecular interactions as a function of composition (χTFSI indicating the mole fraction of the added compound). It is found that on addition of [C2HIm][TFSI] to [C2HIm][TfO], the melting temperature is first decreased (0 (Formula presented.) 0.3) and then suppressed (0.3 (Formula presented.) 0.8) resulting in mixtures with no phase transitions. These mixtures display a wide temperature range of the liquid state and should be interesting for use in devices operating at extreme temperatures. The ionic conductivity does not vary significantly across the composition range analyzed, as evidenced in the comparative Arrhenius plot. The activation energy, Ea, estimated by fitting with the Arrhenius relation in a limited temperature range (between 60 and 140 °C) varies marginally and keeps values between 0.17 and 0.21 eV. These marginal differences can be rationalized by the initially very similar values of the two neat protic ionic liquids. Vibrational spectroscopy, including both Raman and infrared spectroscopies, reveals weakening of the cation–anion interactions for increasing content of [C2HIm][TFSI], which is reflected by the blue shift of the average N-H stretching mode and the red shift of the S-O stretching mode in the TfO anion. These trends correlate with the higher disorder in the mixtures observed by DSC and are evidenced by the decrease and suppression of the melting temperature as the amount of [C2HIm][TFSI] is increased.
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| 2. |
- Dai, Zhengxing, et al.
(författare)
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Screening ionic liquids for developing advanced immobilization technology for CO2 separation
- 2022
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Ingår i: Frontiers in Chemistry. - : Frontiers Media S.A.. - 2296-2646. ; 10
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Tidskriftsartikel (refereegranskat)abstract
- Developing immobilized-ionic liquids (ILs) sorbents is important for CO2 separation, and prior theoretically screening ILs is desirable considering the huge number of ILs. In this study, the compressibility of ILs was proposed as a new and additional index for screening ILs, and the developed predictive theoretical model, i.e., electrolyte perturbed-chain statistical associating fluid theory, was used to predict the properties for a wide variety of ILs in a wide temperature and pressure range to provide systematic data. In screening, firstly, the isothermal compressibilities of 272 ILs were predicted at pressures ranging from 1 to 6,000 bar and temperatures ranging from 298.15 to 323.15 K, and then 30 ILs were initially screened. Subsequently, the CO2 absorption capacities in these 30 ILs at temperatures from 298.15 to 323.15 K and pressures up to 50 bar were predicted, and 7 ILs were identified. In addition, the CO2 desorption enthalpies in these 7 ILs were estimated for further consideration. The performance of one of the screened ILs was verified with the data determined experimentally, evidencing that the screen is reasonable, and the consideration of IL-compressibility is essential when screening ILs for the immobilized-IL sorbents.
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| 3. |
- Engelbrecht, Leon de Villiers, et al.
(författare)
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MD simulations explain the excess molar enthalpies in pseudo-binary mixtures of a choline chloride-based deep eutectic solvent with water or methanol
- 2022
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Ingår i: Frontiers in Chemistry. - : Frontiers Media S.A.. - 2296-2646. ; 10
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Tidskriftsartikel (refereegranskat)abstract
- The addition of molecular liquid cosolvents to choline chloride (ChCl)-based deep eutectic solvents (DESs) is increasingly investigated for reducing the inherently high bulk viscosities of the latter, which represent a major obstacle for potential industrial applications. The molar enthalpy of mixing, often referred to as excess molar enthalpy HE—a property reflecting changes in intermolecular interactions upon mixing—of the well-known ChCl/ethylene glycol (1:2 molar ratio) DES mixed with either water or methanol was recently found to be of opposite sign at 308.15 K: Mixing of the DES with water is strongly exothermic, while methanol mixtures are endothermic over the entire mixture composition range. Knowledge of molecular-level liquid structural changes in the DES following cosolvent addition is expected to be important when selecting such “pseudo-binary” mixtures for specific applications, e.g., solvents. With the aim of understanding the reason for the different behavior of selected DES/water or methanol mixtures, we performed classical MD computer simulations to study the changes in intermolecular interactions thought to be responsible for the observed HE sign difference. Excess molar enthalpies computed from our simulations reproduce, for the first time, the experimental sign difference and composition dependence of the property. We performed a structural analysis of simulation configurations, revealing an intriguing difference in the interaction modes of the two cosolvents with the DES chloride anion: water molecules insert between neighboring chloride anions, forming ionic hydrogen-bonded bridges that draw the anions closer, whereas dilution of the DES with methanol results in increased interionic separation. Moreover, the simulated DES/water mixtures were found to contain extended hydrogen-bonded structures containing water-bridged chloride pair arrangements, the presence of which may have important implications for solvent applications.
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| 4. |
- Fan, Han, 1989-, et al.
(författare)
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Ensemble Learning-Based Approach for Gas Detection Using an Electronic Nose in Robotic Applications
- 2022
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Ingår i: Frontiers in Chemistry. - : Frontiers Media S.A.. - 2296-2646. ; 10
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Tidskriftsartikel (refereegranskat)abstract
- Detecting chemical compounds using electronic noses is important in many gas sensing related applications. A gas detection system is supposed to indicate a significant event, such as the presence of new chemical compounds or a noteworthy change of concentration levels. Existing gas detection methods typically rely on prior knowledge of target analytes to prepare a dedicated, supervised learning model. However, in some scenarios, such as emergency response, not all the analytes of concern are a priori known and their presence are unlikely to be controlled. In this paper, we take a step towards addressing this issue by proposing an ensemble learning-based approach (ELBA) that integrates several one-class classifiers and learns online. The proposed approach is initialized by training several one-class models using clean air only. During the sampling process, the initialized system detects the presence of chemicals, allowing to learn another one-class model and update existing models with self-labelled data. We validated the proposed approach with real-world experiments, in which a mobile robot equipped with an e-nose was remotely controlled to interact with different chemical analytes in an uncontrolled environment. We demonstrated that the ELBA algorithm not only can detect gas exposures but also recognize baseline responses under a suspect short-term sensor drift condition. Depending on the problem setups in practical applications, the present work can be easily hybridized to integrate other supervised learning models when the prior knowledge of target analytes is partially available.
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| 5. |
- Foorginezhad, Sahar, et al.
(författare)
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Reviewing and screening ionic liquids and deep eutectic solvents for effective CO2 capture
- 2022
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Ingår i: Frontiers in Chemistry. - : Frontiers Media S.A.. - 2296-2646. ; 10
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Forskningsöversikt (refereegranskat)abstract
- CO2 capture is essential for both mitigating CO2 emissions and purifying/conditioning gases for fuel and chemical production. To further improve the process performance with low environmental impacts, different strategies have been proposed, where developing liquid green absorbent for capturing CO2 is one of the effective options. Ionic liquids (IL)/deep eutectic solvents (DES) have recently emerged as green absorbents with unique properties, especially DESs also benefit from facile synthesis, low toxicity, and high biodegradability. To promote their development, this work summarized the recent research progress on ILs/DESs developed for CO2 capture from the aspects of those physical- and chemical-based, and COSMO-RS was combined to predict the properties that are unavailable from published articles in order to evaluate their performance based on the key properties for different IL/DES-based technologies. Finally, top 10 ILs/DESs were listed based on the corresponding criteria. The shared information will provide insight into screening and further developing IL/DES-based technologies for CO2 capture.
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| 6. |
- Huang, Jinshu, et al.
(författare)
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Research Progress on the Photo-Driven Catalytic Production of Biodiesel
- 2022
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Ingår i: Frontiers in Chemistry. - : Frontiers Media SA. - 2296-2646. ; 10
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Forskningsöversikt (refereegranskat)abstract
- Biodiesel considered a green, environmentally friendly, and renewable energy source is one of the most promising candidates to replace fossil fuels to supply energy for the world. The conventional thermocatalytic methods have been extensively explored for producing biodiesel, while inevitably encountering some drawbacks, such as harsh operating conditions and high energy consumption. The catalytic production of biodiesel under mild conditions is a research hotspot but with difficulty. Photocatalysis has recently been highlighted as an eco-friendly and energy-saving approach for biodiesel production. This mini-review summarizes typical photocatalysts for biodiesel production and discusses in detail the catalytic mechanism and strategies of the photo-driven (trans)esterification to produce biodiesel. The current challenges and future opportunities of photo-driven catalysis to prepare biodiesel are also outlined, in steps towards guiding the design of advanced photocatalysts for biodiesel production.
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| 7. |
- Larsson, Ernst D., et al.
(författare)
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Convergence of Electronic Structure Properties in Ionic Oxides Within a Fragment Approach
- 2022
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Ingår i: Frontiers in Chemistry. - : Frontiers Media SA. - 2296-2646. ; 10
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Tidskriftsartikel (refereegranskat)abstract
- Embedded-cluster models of crystalline solids are important to allow accurate wave function methods to be applicable to solids. The ab-initio model potential method, in which the crystal is divided into three different fragments, one quantum fragment, one ab-initio model potential fragment and one point-charge fragment, has historically been shown to be a viable tool for describing the electronic structure in ionic solids. The optimal size of these regions is, of course, individual for each crystal. In this study we analyzed the convergence of the electronic structure properties with respect to an increase of the size of the quantum part and the layer of potentials. MgO crystal and Ni: MgO were used for this purpose as examples of an ideal crystal and a crystal with a point defect. We demonstrated that with an increase of the cluster size, the electron density in the inner part of the cluster becomes very similar to the electron density in the periodic model. Clusters, embedded into a layer of model potential and electrostatic field, are a good alternative to periodic description.
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| 8. |
- Lellala, Kashinath, et al.
(författare)
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Ceria Boosting on In Situ Nitrogen-Doped Graphene Oxide for Efficient Bifunctional ORR/OER Activity
- 2022
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Ingår i: Frontiers in Chemistry. - : Frontiers Media S.A.. - 2296-2646. ; 10
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Tidskriftsartikel (refereegranskat)abstract
- In the present work, a highly efficient and excellent electrocatalyst material for bifunctional oxygen reduction/evolution reaction (ORR/OER) was synthesized using the microwave-assisted hydrothermal method. In brief, ultrafine hexagonal cerium oxide (CeO2) nanoparticles were tailored on the layered surface of in situ nitrogen-doped graphene oxide (NGO) sheets. The nanocomposites exhibited a high anodic onset potential of 0.925 V vs. RHE for ORR activity and 1.2 V for OER activity with a very high current density in 0.5 M KOH. The influence of oxygen cluster on Ce3+/Ce4+ ion decoration on outward/inward in situ nitrogen-coupled GO enhanced the physicochemical properties of composites and in turn increased electron transferability. The microwave-assisted hydrothermal coupling technique provides a higher density, active sites on CeO2@NGO composites, and oxygen deficiency structures in ultrafine Ce-O particles and boosts higher charge transferability in the composites. It is believed that the physical states of Ce-N- C, Ce-C=O, and a higher amount of oxygen participation with ceria increase the density of composites that in turn increases the efficiency. N-doped graphene oxide promotes high current conduction and rapid electron transferability while reducing the external transport resistance in oxygen electrocatalysis by sufficient mass transfer through in-built channels. This study may provide insights into the knowledge of Ce-enabled bifunctional activity to guide the design of a robust catalyst for electrochemical performance.
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| 9. |
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| 10. |
- Mashindi, Victor, et al.
(författare)
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Platinum Nanocatalysts Supported on Defective Hollow Carbon Spheres : Oxygen Reduction Reaction Durability Studies
- 2022
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Ingår i: Frontiers in Chemistry. - : Frontiers Media SA. - 2296-2646. ; 10
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Tidskriftsartikel (refereegranskat)abstract
- The durability and long-term applicability of catalysts are critical parameters for the commercialization and adoption of fuel cells. Even though a few studies have been conducted on hollow carbon spheres (HCSs) as supports for Pt in oxygen reduction reactions (ORR) catalysis, in-depth durability studies have not been conducted thus far. In this study, Pt/HCSs and Pt/nitrogen-doped HCSs (Pt/NHCSs) were prepared using a reflux deposition technique. Small Pt particles were formed with deposition on the outside of the shell and inside the pores of the shell. The new catalysts demonstrated high activity (>380 μA cm−2 and 240 mA g−1) surpassing the commercial Pt/C by more than 10%. The catalysts demonstrated excellent durability compared to a commercial Pt/C in load cycling, experiencing less than 50% changes in the mass-specific activity (MA) and surface area-specific activity (SA). In stop-start durability cycling, the new materials demonstrated high stability with more than 50% retention of electrochemical active surface areas (ECSAs). The results can be rationalised by the high BET surface areas coupled with an array of meso and micropores that led to Pt confinement. Further, pair distribution function (PDF) analysis of the catalysts confirmed that the nitrogen and oxygen functional groups, as well as the shell curvature/roughness provided defects and nucleation sites for the deposition of the small Pt nanoparticles. The balance between graphitic and diamond-like carbon was critical for the electronic conductivity and to provide strong Pt-support anchoring.
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